US10294167B2 - Recovery of phosphorous - Google Patents
Recovery of phosphorous Download PDFInfo
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- US10294167B2 US10294167B2 US15/414,116 US201715414116A US10294167B2 US 10294167 B2 US10294167 B2 US 10294167B2 US 201715414116 A US201715414116 A US 201715414116A US 10294167 B2 US10294167 B2 US 10294167B2
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- MWQKURVBJZAOSC-UHFFFAOYSA-N CC(C)C1=CC=CC1 Chemical compound CC(C)C1=CC=CC1 MWQKURVBJZAOSC-UHFFFAOYSA-N 0.000 description 1
- NFWSQSCIDYBUOU-UHFFFAOYSA-N CC1=CC=CC1 Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Cc1ccccc1 Chemical compound Cc1ccccc1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
- C02F1/385—Treatment of water, waste water, or sewage by centrifugal separation by centrifuging suspensions
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B15/00—Organic phosphatic fertilisers
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D3/00—Calcareous fertilisers
- C05D3/02—Calcareous fertilisers from limestone, calcium carbonate, calcium hydrate, slaked lime, calcium oxide, waste calcium products
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
- C05D9/02—Other inorganic fertilisers containing trace elements
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F11/00—Other organic fertilisers
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/127—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering by centrifugation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/02—Softening water by precipitation of the hardness
- C02F5/06—Softening water by precipitation of the hardness using calcium compounds
Definitions
- the present invention is in the field of an improved method for recovery of phosphorous, in particular of phosphorous from a waste stream, and to a product obtained thereby.
- the product is in a form wherein phosphorous can be released to, e.g., the soil and plants at a desired amount per interval of time.
- Phosphorous is an element (P) that is used abundantly especially for growing crops, such as by adding fertilizer. To stress the significance of phosphorous it is noted that P fertilizer is essential for modern food production and is the limiting factor in crop yields. P is a critical global resource, as are water and energy resources. Phosphorus is considered essential for all living matter, including bacteria, plants and animals.
- Phosphate rock used as a source for P in fertilizers, clearly is a non-renewable resource that are likely to be depleted in 50-100 years, so there is a need to reuse phosphorus. Production peak is expected in about twenty years' time. Unlike other natural resources phosphorus has no substitute in food production. In view of a growing food demand such is even more of a concern. It is also noted that mining (of phosphate) is an energy intensive and polluting activity. Such will become even worse as the quality of phosphate rock is declining ([P 2 O 5 ] in mined rock is decreasing and the concentration of associated heavy metals is increasing). It is noted that in principle heave metals need to removed, if applied as fertilizer, which is at the least energy intensive. One may conclude based on the above that cheap fertilizer is an element of the past. Alternative strategies need to be developed, as is the case.
- US2013/0299420 A1 recites a method for recovering phosphate from sewage treatment plants using multi-stage anaerobic digestion includes the treatment of organic acid digest with calcium hydroxide, calcium oxide, and similar compounds to raise pH to near neutral values and precipitate calcium phosphate compounds such as brushite and similar amorphous compounds.
- the method includes the formation of calcium phosphates on weak-acid ion exchange columns and membranes in contact with organic acid digest.
- the system includes removal of the calcium phosphate compounds formed by sedimentation, either static or against an upwelling flow, centrifugation, or filtration. Under ideal conditions and surplus of calcium 50-90% (15/17 or ⁇ 88%) of the phosphate may be captured, i.e., 10-40% remains in the sewage; these conditions are typically not reached, so incomplete capturing of phosphate occurs.
- EP 2 511 243 A1 recites a plant for phosphate removal from wastewater in a continuous operation, comprising a substantially cylindrical stirred reactor, which is charged with calcium silicate hydrate (CSH) as a crystallization substrate and a sedimentation container, where the stirred reactor is divided into a resting zone, which is located in the upper part and a reaction zone which is located in the lower part.
- CSH calcium silicate hydrate
- a reaction with phosphate comprising waste water
- three phosphate minerals are claimed to be formed, namely hydroxyl apatite, struvite (NH 4 MgPO 4 .6H 2 O), and brushite.
- the “P-elimination” in FIG. 2 shows a % between about 35% and 90% (or 65%-10% loss), for some reason depending on a reactor volume; such seems to reflect that the process is not scalable.
- FIG. 3 provides even worse results as a function of reaction time.
- the CSH materials are the main product of the hydration of Portland cement and are characterized by a typically complex structure and ratio between components, wherein a relative amount of Ca and Si are given and the oxygens are attributed to Ca and Si (or complexes thereof). Therein no individual Cao, SiO 2 or hydrate can be distinguished; Ca, Si, H and O are part of a large complex, comparable to a crystal.
- CSH materials may be used for pozzolanic reactions.
- the pozzolanic reaction is a chemical reaction that occurs in portland cement containing pozzolans.
- the pozzolanic reaction relates to a simple acid-base reaction between calcium hydroxide, also known as Portlandite, or (Ca(OH) 2 ), and silicic acid (H4SiO 4 , or Si(OH) 4 ); it is not performed in an aqueous environment. This has nothing to do with the present invention, but relates to a different field of technology, namely cement formation.
- the present invention relates to an improved method for recovering phosphorous from an aqueous solution.
- the present method reduces losses from about 10-40% of prior art methods to less than 1%.
- the present method has been found to be insensitive to impurities, such as heavy metals and organic material.
- the present method makes use of cheap reactants, such as CaO, clay and CaCO 3 , in low amounts, which reactants are present as a mixture of ingredients; such is clearly different in chemical and physical aspects from a composition having a similar amount and/or ratio of chemical elements (e.g., Ca, C, O, Al, Si) being present, as the person skilled in the art will appreciate.
- chemical elements e.g., Ca, C, O, Al, Si
- Clay minerals are hydrous aluminium phyllosilicates, sometimes with variable amounts of iron, magnesium, alkali metals, alkaline earths, and other cations; clays are considered to comprise SiO 4 units and AlO 4 units.
- a CSH is not a clay nor does it resemble a clay.
- the present method has been found to be robust, e.g., it can handle almost any aqueous solution, such as waste streams.
- the present method provides phosphate largely (>90%) in the form of brushite (instead of prior art struvite); brushite is a phosphate mineral that can be used in agriculture directly, due to its favorable uptake characteristics, and can be reprocessed into high-grade phosphorous ore.
- the present method can be performed at ambient temperature and pressure; hence besides reactants no reaction costs are involved. Surprisingly the efficiency of the present process is higher than could “theoretically” be expected.
- the present method can be operated in a continuous or semi continuous mode, making it possible to process continuous flows without problem at a relatively constant output.
- the process is also scalable, hence small and large volumes can be processed.
- the present composition comprises 5-40% CaO (w/w, also weight percentages are taken relative to a total weight of the composition, unless stated otherwise), 10-40% clay mineral, and 20-60% CaCO 3 .
- about 0.5-20 gr of the composition was added relative to 1 gr of soluble phosphate, such as 1-10 gr composition.
- the amount of composition is calculated based on an amount of CaO: 0.5-2 mole CaO/mole soluble P is added, which is close to 1 mole CaO per mole soluble P. Such depends a bit on the characteristics of the aqueous solution. It comes as a surprise that under relatively harsh conditions relatively small amounts of the present composition suffice for recovering the phosphorous.
- the phosphorous settles easily and can then be recovered.
- the present invention provides a solution to one or more of the above mentioned problems and overcomes drawbacks of the prior art.
- the present invention relates to an improved method of recovering phosphorous from an aqueous solution comprising the steps of providing the aqueous solution comprising soluble phosphorous, adding a composition, the composition comprising 5-40% CaO (w/w, relative to a total weight of the composition), 10-40% clay mineral, and 20-60% CaCO 3 , wherein 0.5-2 mole CaO/mole soluble P is added, and recovering the phosphorous.
- the solution is an acidic solution, the acid aqueous solution having a pH of 1-6, wherein the pH is increased to 5.5-8 by adding the composition.
- the solution is a basic solution.
- an amount of soluble phosphorous present is in a range of 1-50 ppm (mg/l). In a further example an amount of soluble phosphorous present is in a range of 100-1000 ppm (mg/l). In a further example an amount of soluble phosphorous present is in a range of 10-250 g/l.
- the present method is capable of reducing losses in (very) low soluble P concentration solutions to less than 20% and typically less than 10%; hence it is still worthwhile to strip such solutions from small amounts of phosphorous being present therein.
- the present method is capable of reducing losses in (very) high soluble P concentration solutions to less than 1%; such is in view of the prior art a major step forward. In an example the present method may be performed more than once, especially for relatively high concentration solutions, e.g., first recovering almost all of the phosphorous, and then recovering a majority of what is left in the first step. As such losses can be reduced to less than 0.2%.
- the clay mineral is selected from a natural or artificial clay, the clay preferably being a monovalent cation clay, comprising one or more of H+, Na+, K+, Li+, such as a TOT-clay (or 2:1 clay) or T-O clay (1:1 clay), such as a kaolin clay, such as kaolinite, dickite, halloysite and nacrite, a smectite clay, such as bentonite, montmorillonite, nontronite and saponite, an illite clay, a chlorite clay, a silicate mineral, such as mica, such as biotite, lepidolite, muscovite, phlogopite, zinnwaldite, clintonite, and allophane.
- a TOT-clay (or 2:1 clay) or T-O clay (1:1 clay) such as a kaolin clay, such as kaolinite, dickite, halloysite and nacrite,
- Kaolinite is a clay mineral, part of the group of industrial minerals, with the chemical composition Al 2 Si 2 O 5 (OH) 4 . From kaolinite endothermic dehydroxylation (or alternatively, dehydration) beginning at 550-600° C. produces disordered meta-kaolin, Al 2 Si 2 O 7 . Meta-kaolin is not a simple mixture of amorphous silica (SiO 2 ) and alumina (Al 2 O 3 ), but rather a complex amorphous structure that retains some longer-range order (but not strictly crystalline) due to stacking of its hexagonal layers. A large use is in the production of paper, including ensuring the gloss on some grades of paper.
- kaolin and meta-kaolin are considered as silica-alumina compounds also forming part of a sorbent obtained from paper-waste or the like.
- the clay preferably has a cationic exchange capacity of 2-200 meq/100 grams clay at a pH of 7, more preferably 5-150 meq/100 grams, even more preferably 10-120 meq/100 grams. It has been found that clays having a relatively higher CEC perform better in terms of relevant characteristics for the present invention.
- the composition comprises 10-35% CaO (w/w), preferably 20-30% CaO (w/w), such as from 25-28% (w/w), 15-35% (w/w) (meta)kaolin, that may or may not be in the dehydrated form of meta-kaolin, preferably from 20-30% (w/w), such as from 25-27% (meta)kaolin (w/w), and 25-50% CaCO 3 (w/w), preferably 30-45% (w/w), such as from 35-40% (w/w). It has been found that with the above example very good results were obtained, e.g., in terms of losses of phosphorous.
- the composition is obtained by thermal conversion of a material chosen from paper waste and residue from the paper production, such as TopCreteTM.
- This latter composition performs exceptionally well, e.g., gives higher yields, can be recycled as such by use in the present method, and above all is cheap.
- This is at least surprising, as this composition relates to a waste product, which waste products performs even better than virgin materials. Note that from an economical point of view mixing the ingredients of the present composition is not feasible.
- puzzolanic material containing metakaolinite and calcium oxide converted into calcium hydroxide. Careful control of the process conditions avoids that the produced metakaolinite is converted into a material of poorer puzzolanic properties. Further, the puzzolanic material obtained only contains a limited amount of calcium oxide, which oxide, in contrast with the hydroxide, has adverse effects on the strength of the concrete and hardened cement manufactured with puzzolanic material.
- the kaolin-containing material used is preferably waste paper or residues that stem from recycling of waste paper for reuse in the paper industry. Said residues, which may serve as starting material in the described method, may be inferior paper residue, that is to say paper residue having on average too short a fiber length or sludge from waste water purification plants of the paper industry using waste paper as basic material.
- the above method is characterized in that the temperature of the fluidized bed is 780° C.
- the incineration takes place in a fluidized bed at a temperature of preferably 780° C. wherein the same or a lower temperature prevails in the freeboard.
- the teachings of these documents are referred to for better understanding.
- composition obtained by thermal conversion may vary to some extent over time, and may vary form paper plant to paper plant. However, it has been found that such variation, if controlled, is compatible with the present invention, as is, e.g., detailed in the present claims.
- the aqueous solution is selected from waste water, treated waste water, sludge, organic acid digest solution, acid digest solution, animal manure, such as pig manure, cow manure, chicken litter, and combinations thereof.
- animal manure such as pig manure, cow manure, chicken litter, and combinations thereof.
- the aqueous solution comprises 0.01-6 wt. % solids.
- polluted waste streams can still be treated, albeit typically at the consequence of having a part of the solids of the solution in the recovered product. Such may not be a concern, however.
- the aqueous solution may be treated further.
- an organic acid digest may be treated for phosphorus recovery before it is added to a thermophilic or mesophilic digester.
- Such treatment may relate to additional screening, floatation, sedimentation, filtration, or centrifugation of large particles in the digest before phosphate removal from the remaining liquid portion.
- a resulting calcium phosphate product may be collected by sedimentation (either static sedimentation in a settling tank or sedimentation in an upwelling flow as in a fluidized bed reactor), filtration, or centrifugation.
- the processed organic digest may be sent to the thermophilic digester for methanogenesis.
- an organic acid digest either with or without particle removal, may be applied to an ion exchange column loaded with, e.g., the present composition. Operation will be much like that of standard ion-exchange columns used for water softening. After the column is spent, resulting calcium phosphate particles in the column may be removed by backwashing with tap water or plant effluent. The column can be regenerated. Further, an organic acid digest is treated for phosphorus recovery and returned to the organic acid digester. As in the first and second embodiments, additional screening, floatation, sedimentation, filtration, or centrifugation of large particles in the digest is permitted before phosphate removal from the remaining liquid portion. Phosphate recovery will be effected by either reaction with the present composition.
- the aqueous solution comprises impurities, such as heavy metals, organic matter, and humus; despite these impurities still good results are obtained.
- impurities such as heavy metals, organic matter, and humus
- the present method is for forming brushite (CaHPO 4 .2H 2 O), wherein the brushite precipitates, and wherein the precipitate is recovered and optionally dried.
- brushite is a preferred phosphate mineral for agricultural applications.
- 50-90% of the phosphate is recovered as brushite. It is considered that this percentage can be optimized further. Such is compared to several prior art methods also an advantage, as often the mineral struvite is obtained.
- the pH is increased to 6-7, preferably to 6.2-6.7.
- the CaO is sufficient to establish such an increase, even if the pH of the solution is relatively low. So also in this respect the present method is robust.
- the composition comprising CaO, the clay mineral, and CaCO 3 is homogeneously distributed. That is particle sizes and composition per unit volume or unit surface varies over a narrow distribution. Such a composition provides the present results.
- the present composition such as TopCreteTM
- BET Brunauer-Emmett-Teller
- the present composition preferably has a particle size distribution (laser granulometric, ISO13320 (2009), e.g. Malvern, Mastersizer 3000) of 90% smaller than 50 ⁇ m, 80% smaller than 30 ⁇ m, 50% smaller than 10 ⁇ m, and 30% smaller than 3 ⁇ m.
- the present invention relates to a product obtained by the present method, comprising (on an atom/atom basis) 40-70% brushite)(CaHPO 4 .2H 2 O, preferably 45-65%, such as 50-55%, 10-30% calcite (CaCO 3 ), preferably 12-25%, such as 15-20%, 1-10% meta-kaoline (Al 2 Si 2 O 7 ), preferably 2-8%, such as 3-7%, 0.1-20% Mg phosphate)(MgHPO 4 .2H 2 O, preferably 0.2-15%, such as 0.5-10%, and preferably ⁇ 1000 ppm (mg/kg) heavy metals (As, Cd, Cr, Co, Cu, Pb, Hg, Mb, Ni, Se, and Zn), e.g.
- a product obtained by the present method comprising (on an atom/atom basis) 40-70% brushite)(CaHPO 4 .2H 2 O, preferably 45-65%, such as 50-55%, 10-30%
- the present invention relates to a use of the present product as a fertilizer.
- This has been found to give advantages over the prior art products.
- a fertilizer is readily available, hence being well soluble, whereas in view of leaching the product is hardly soluble; the present product is found to be readily available to plants and not to leach, which came as a surprise. Possibly this is a consequence of the way the product is made, i.e., the present method, which may be slightly acidic. Leaching is found to be more prone for phosphate compositions that were made using a method at a pH from 8-10.
- the further components e.g., CaCaO 3 and clay are not toxic and contribute especially in cases of acid soils to the soil quality and availability to plants of the fertilizer. Due to presence of these further components a relative percentage of phosphorous is lower compared to, e.g., use of Ca(OH) 2 .
- MgHPO 4 .2H 2 O In addition to clay and calcite also some Mg phosphate, most likely MgHPO 4 .2H 2 O, is typically formed, due to presence of some Mg in the present composition.
- FIG. 1 Experimental configuration of a brushite recovery process.
- FIG. 1 is further detailed, in as far as relevant, below.
- Organic acid digest is a product of an initial step of a multi-phase, multi-temperature anaerobic digestion process used at some wastewater treatment plants, often with the intention of reducing solids loading and increasing biogas generation. Within the 1 to 4-day retention time, acidogenesis and acetogenesis occur, resulting in a digest containing high concentrations of volatile fatty acids, an acid pH, and high concentrations of soluble phosphorus.
- TopCreteTM was tested in the second of five batch brushite recovery trials at Madison Metropolitan Sewerage District (MMSD).
- Organic acid digest was produced in a custom-built 208-L digester with a 50/50 (v/v) mixture of primary sludge and activated sludge. The sludge was held for ten days at a four-day residence time until the pH stabilized.
- the digest having a pH of 5.46, a temperature of 37° C., and 4.38 wt. % solids, was then mixed with a flocculent and pumped through a decanter centrifuge (Table 1). See FIG. 1 for process configuration.
- a first experiment relates to laboratory jar tests: such provides an initial assessment of how TopCreteTM could perform on a larger scale.
- Organic acid centrate was collected in triplicate 1-L jars and sufficient TopCreteTM was added to raise the pH to 6.5.
- Initial and final samples of the centrate were analyzed by ICP.
- the centrate used for the jar tests initially contained 731 ppm (mg/l) of soluble phosphorus with 0.40% solids (Table 3 and Table 4). Addition of TopCreteTM to the centrate reduced the soluble phosphorus to a final 215 ppm, a 71% reduction. The TopCreteTM and brushite settled out of solution easily. For an initial test such a reduction is considered promising. Chemical analysis indicated 11.3% P in the recovered precipitate of the jar test, equivalent to 25.9% P 2 O 5 (Table 5) if expressed in oxide format.
- Centrate for the batch trial initially contained 715 ppm phosphorus with 0.46% solids (Table 3 and Table 4). TopCreteTM successfully precipitated brushite and settled as easy as in the jar tests. Centrate phosphate was reduced from an initial value of 715 ppm P to 2 (sic! ppm, a 99% reduction in the soluble phosphorus (Table 4). The phosphorus content of the precipitate was 8.8% P, or 20.2% P 2 O 5 (Table 5) if expressed in oxide format.
- TopCreteTM performed well in reducing soluble P in the organic acid digests, with a 71% reduction in soluble phosphorus during the jar test and a 99% reduction in the batch trial. The resulting material settled well and had a P content of 11.3 and 8.8% in the jar and batch tests, respectively. It is noted that pure brushite, CaHPO 4 .H 2 O, has a P content of 18%, indicating some “dilution” of brushite with the adjunct minerals in TopCreteTM that carried through to the precipitate. These results indicate very promising potential use of TopCreteTM as a source material for a phosphorus recovery and upcycling process.
- Trials 1 and 3-5 relate to a Ca(OH) 2 composition, whereas trial 2 relates to use of Toperete (a composition according to claim 1 ), giving besides the highest recovery (99%) also almost the highest availability.
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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NL2013253 | 2014-07-24 | ||
NL2013253A NL2013253B1 (en) | 2014-07-24 | 2014-07-24 | Recovery of phosphorous. |
PCT/NL2015/050519 WO2016013929A2 (fr) | 2014-07-24 | 2015-07-15 | Récupération de phosphore |
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Application Number | Title | Priority Date | Filing Date |
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PCT/NL2015/050519 Continuation WO2016013929A2 (fr) | 2014-07-24 | 2015-07-15 | Récupération de phosphore |
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US20170129819A1 US20170129819A1 (en) | 2017-05-11 |
US10294167B2 true US10294167B2 (en) | 2019-05-21 |
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WO2021006737A1 (fr) | 2019-07-10 | 2021-01-14 | Cdem B.V. | Récupération de phosphore |
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NL2013253B1 (en) | 2014-07-24 | 2016-09-09 | Cdem B V | Recovery of phosphorous. |
AU2017339955A1 (en) | 2016-10-05 | 2019-04-11 | Nutrient Recovery & Upcycling, Llc | Wastewater treatment with customized phosphate control |
CN106865651A (zh) * | 2017-03-28 | 2017-06-20 | 安徽中煦环保新材料科技有限公司 | 一种高效废水净化修复剂及其制备方法 |
US11306269B2 (en) * | 2017-12-04 | 2022-04-19 | Gmt Ip, Llc | Processing post-industrial and post-consumer waste streams and preparation of post-industrial and post-consumer products therefrom |
CN108996885A (zh) * | 2018-08-27 | 2018-12-14 | 华南理工大学 | 一种蒙脱石型氧化污泥脱水剂及其制备方法和应用 |
WO2020160426A1 (fr) * | 2019-01-31 | 2020-08-06 | Wisconsin Alumni Research Foundation | Procédé de fabrication d'acide phosphorique à partir de minerais de phosphate |
EP4281416A1 (fr) * | 2021-01-25 | 2023-11-29 | Migal Galilee Research Institute Ltd. | Compositions fertilisantes et leurs procédés d'utilisation |
CN114684967A (zh) * | 2022-04-06 | 2022-07-01 | 深圳大学 | 钙质固废与含磷废液协同处理方法及其产物的应用 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021006737A1 (fr) | 2019-07-10 | 2021-01-14 | Cdem B.V. | Récupération de phosphore |
NL2023467B1 (en) | 2019-07-10 | 2021-02-02 | Cdem B V | Recovery of phosphorous |
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WO2016013929A2 (fr) | 2016-01-28 |
WO2016013929A3 (fr) | 2016-03-17 |
WO2016013929A4 (fr) | 2016-05-06 |
US20170129819A1 (en) | 2017-05-11 |
NL2013253B1 (en) | 2016-09-09 |
EP3172172A2 (fr) | 2017-05-31 |
CA2991021C (fr) | 2021-07-27 |
CA2991021A1 (fr) | 2016-01-28 |
EP3172172B1 (fr) | 2021-01-06 |
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